Optimization of chromatographic conditions and comparison of extraction efficiencies of four different methods for determination and quantification of pesticide content in bovine milk by UFLC-MS/MS

This paper describes the optimization of a multiresidue chromatographic analysis for the identification and quantification of 20 pesticides in bovine milk, including three carbamates, a carbamate oxime, six organophosphates, two strobilurins, a pyrethroid, an oxazolidinedione, an aryloxyphenoxypropionate acid/ester, a neonicotinoid, a dicarboximide, and three triazoles. The influences of different chromatographic columns and gradients were evaluated. Furthermore, four different extraction methods were evaluated; each utilized both different solvents, including ethyl acetate, methanol, and acetonitrile, and different workup steps. The best results were obtained by a modified QuEChERS method that lacked a workup step, and that included freezing the sample for 2 hours at -20 ºC. The results were satisfactory, yielding coefficients of variation of less than 20%, with the exception of the 50 µg L-1 sample of famoxadone, and recoveries between 70 and 120%, with the exception of acephate and bifenthrin; however, both analytes exhibited coefficients of variation of less than 20%.

CARACTERIZAÇÃO E ATIVIDADE CATALÍTICA DE K2CO3/AL2O3 NA TRANSESTERIFICAÇÃO DO ÓLEO DE GIRASSOL COM AQUECIMENTO CONVENCIONAL E MICRO-ONDAS

Commercial and synthetic mesoporous aluminas impregnated with potassium carbonate were characterized by X-ray diffraction (XRD), nitrogen physisorption, infrared spectroscopy and 27Al MAS NMR. The activities in the transesterification reaction of sunflower oil with methanol for biodiesel production were evaluated. 27Al MAS NMR spectra evidenced the presence of AlIV and AlVI in the samples, and also of AlV sites in the mesoporous synthesized alumina, which disappeared after impregnation with potassium salt followed by calcination. All aluminas containing potassium were active for biodiesel production from sunflower seed oil, with high conversions by both conventional heating and microwave irradiation.

KIT COLORIMÉTRICO PARA DETECÇÃO DE METANOL EM ETANOL COMBUSTÍVEL PARA O MONITORAMENTO DA QUALIDADE DE COMBUSTÍVEIS

A colorimetric kit for methanol detection in ethanol-containing fuels and ease of use in the field was developed and tested. The analysis can detect the presence of methanol in fuels when exceeding specification (0.5% v/v) in about 20 min and its simple instrumentation does not require a specialist. The kit method was successfully validated at gas stations located in São Paulo State and the Federal District.

COMPOSIÇÃO QUÍMICA E TEMPERATURA DE CRISTALIZAÇÃO DE ÉSTERES OBTIDOS DE QUATRO ÓLEOS VEGETAIS EXTRAÍDOS DE SEMENTES DE PLANTAS DO CERRADO

The seed oils from four plants (Scheelea phalerata, Butia capitata, Syagrus romanzoffiana, Terminalia cattapa) found in Mato Grosso do Sul were extracted at good yields. Alkaline transesterification of these seed oils to esters using methanol and ethanol was studied and also produced good yields. Oleic acid (30.5/32.3%), lauric acid (30.7/32.9%) methyl and ethyl esters, were the main components of transesterification of the oils from Scheelea phalerata and Syagrus romanzoffiana. Lauric acid (42.2%), capric acid (15.9%) and caprylic acid (14.6%) methyl and ethyl esters were the main ester components of transesterification of the oil from Butia capitata. Oleic acid (37.8%), palmitic acid (33.5%) and linoleic acid (22.6%) methyl and ethyl esters were the main components of transesterification of oil from Terminalia catappa. Based on differential scanning calorimetry (DSC) studies, the first crystallization peak temperature of esters was observed. Esters derived from oils of the family Arecaceae (Scheelea phalerata, Butia capitata, Syagrus romanzoffiana) showed the lowest points of crystallization, despite having high levels of saturated fat. Esters of Terminalia cattapa oil, rich in unsaturated fat, showed the highest crystallization temperature. This difference in behavior is probably related to the high concentration of esters derived from lauric acid and palmitic acid.

CHEMICAL CONSTITUENTS, ANTI-INFLAMMATORY, AND FREE-RADICAL SCAVENGING ACTIVITIES OF Guettarda viburnoides CHAM. & SCHLTDL. (RUBIACEAE)

Chemical investigation of Guettarda viburnoides (leaves) led to the isolation of ursolic acid, uncaric acid, secoxyloganin, and grandifloroside, along with a mixture of quercetin-3-O-β-D-galactopyranoside and quercetin-3-O-β-D-glucopyranoside, and of β-sitosterol and stigmasterol. The structures of the isolated compounds were elucidated on the basis of their NMR data. The crude extract, ethyl acetate fraction, aqueous-methanol fraction, and grandifloroside showed significant DPPH free-radical scavenging activities with IC50 ranging from 18.92 to 26.47 µg mL-1. The topical administration of the crude extract and fractions markedly reduced the croton oil-induced mice ear edema in 67.0%-99.0%. Inhibition of tissue MPO activity was also observed, which demonstrated an anti-inflammatory effect of the G. viburnoides species.

CHEMICAL COMPOSITION AND ANTI-INFLAMMATORY ACTIVITY OF Roldana platanifolia

The chemical study of Roldana platanifolia led to the isolation of β-caryophyllene, five eremophilanolides, chlorogenic acid, and a mixture of β-sitosterol-stigmasterol, β-sitosteryl glucopyranoside, and sucrose. The anti-inflammatory activities of the extracts and isolated products were tested using the 12-O-tetradecanoylphorbol-13-acetate (TPA) model of induced acute inflammation. The acetone and methanol extracts showed dose dependent activities (ID50 0.21 and 0.32 mg/ear, respectively), while none of the isolated compounds exhibited relevant edema inhibition. The active extracts were also evaluated with the myeloperoxidase assay technique (MPO) to determine their ability to prevent neutrophil infiltration. Results showed that the anti-inflammatory activity was related to the compound’s ability to inhibit pro-inflammatory mediators such as neutrophils.

PRODUÇÃO DE BIODIESEL A PARTIR DE ÁCIDOS GRAXOS PROVENIENTES DO REFINO DE ÓLEOS VEGETAIS VIA CATÁLISE ÁCIDA HETEROGENEA E MICRO-ONDAS

This work presents the biofuel production results of the esterification of fatty acids (C12-C18) and high-acid-content waste vegetable oils from different soap stocks (soybean, palm, and coconut) with methanol, ethanol, and butanol by acid catalysis. We used Amberlyst-35 (A35) sulfonic resin as a heterogeneous acid catalyst and p-toluenesulfonic acid as a homogeneous catalyst for comparison. Both the heterogeneous (A35) and homogeneous (p-toluenesulfonic acid) reactions were performed with 5% w/w of catalyst. The final products were analyzed by proton nuclear magnetic resonance (1H NMR). The homogeneous catalyzed esterification of fatty acids with methanol, ethanol, and butanol produced esters with yields higher than 90%. In the reaction with fatty acids and methanol catalyzed by A35, the best results were achieved with lauric acid and methanol, with a yield of 97%. An increase in the hydrocarbon chain decreased the rate of conversion and yield for stearic acid with methanol, which was 90%. Maximum biodiesel production was achieved from coconut and soybean soap stocks and methanol (96%-98%), which showed conversions very close to those obtained from their respective fatty acids. Microwave irradiation reduced the reaction time from 6 to 1 h in the esterification reaction of fatty acids with butanol.

ESTUDO DA GLICOSILAÇÃO DO CICLO-HEXANOL COM DIFERENTES DERIVADOS DE D-GLICOSAMINA E PROMOTORES DE GLICOSILAÇÃO PELO MÉTODO DE KOENIGS-KNORR

We report herein a study on the glycosylation of cyclohexanol with four D-glucosamine-based peracetylated glycosyl chlorides bearing different substituents at C-2 and three glycosylation promoters, silver carbonate, silver triflate and mercury II chloride/mercury II oxide, by the Koenigs-Knorr method. Under the conditions studied, glycosylation was successful only when 3,4,6-tri-O -acetyl-2-deoxy-2-phthalimido-α-D-glucopyranosyl chloride was used as the glycosyl donor, with silver carbonate proving the best promoter. In order to investigate the influence of the nature of the halogen at C-1, we also carried out the glycosylation of cyclohexanol with 3,4,6-tri-O -acetyl-2-deoxy-2-phthalimido-α-D-glucopyranosyl bromide, a more reactive glycosyl donor. As expected, the yield with the bromide derivative was higher with the three promoters and, again, silver carbonate was the most efficient promoter. Finally, to illustrate the well-known efficient procedure for conversion of the phtalimido group at C-2 to the corresponding acetamido group, cyclohexyl 3,4,6-tri-O -acetyl-2-deoxy-2-phtalimido-β-D-glucopyranoside was converted into cyclohexyl 2-deoxy-2-acetamido-β-D-glucopyranoside in two steps, namely, hydrazinolysis of the phtalimido group followed by chemoselective acetylation of the free amino group by treatment with acetic anhydride in methanol, at 77% overall yield.

ESTIRIL-LACTONAS DE Cryptocarya aschersoniana Mez. (Lauraceae Juss.) COM ATIVIDADE CONTRA Meloidogyne spp. E INTERAÇÃO IN SILICO COM PROVÁVEL FUMARASE DEMeloidogyne hapla

In a previous study, substances with nematicidal properties were detected in the bark of Cryptocarya aschersoniana. Continuing such study, the methanol extract from this plant underwent fractionation guided by in vitro assays with the plant-parasitic nematode Meloidogyne exigua. Two active compounds were isolated and identified by spectroscopic methods as (E)-6-styrylpyran-2-one and (R)-goniothalamin. The latter compound was also active againstMeloidogyne incognita. In silico studies carried out with (R)-goniothalamin and the enzyme fumarate hydratase, which was extracted from the genome of Meloidogyne hapla and modeled using computational methods, suggested that this substance acts against nematodes by binding to a cavity close to the active site of the enzyme.

OTIMIZAÇÃO DO PROCESSO DE TRANSESTERIFICAÇÃO EM DUAS ETAPAS PARA PRODUÇÃO DE BIODIESEL ATRAVÉS DO PLANEJAMENTO EXPERIMENTAL DOEHLERT

In this work, Doehlert experimental design was used to optimize the Transesterification Double Step Process (TDSP) method of methyl soybean oil biodiesel production which starts with a basic catalysis followed by an acidic catalysis. The conversion values were calculated from NMR spectra. Response surface was used to show the results of the interactions between the variables. This experimental design evaluated variables like catalyst and alcohol amount for the basic catalysis and time and temperature for the acidic catalysis. According to results obtained after Doehlert design application the alcohol amount was the main factor that influenced on the basic catalysis but for the acidic catalysis both time and temperature are important and their effects are opposite. It resulted on excellent conversions for both steps obtaining for the basic catalysis about 100% when was used like optimal conditions catalyst amount equal to 0.40 g and volume of methanol equal to 60 mL and for the acidic catalysis about 99% when was used like optimal conditions temperature of 65 °C and 90 minutes for reaction time.

Preparation and electrochemical characterization of Pt nanoparticles dispersed on niobium oxide

Electrodes consisting of Pt nanoparticles dispersed on thin films of niobium oxide were prepared onto titanium substrates by a sol-gel method. The physical characterization of these electrodes was carried out by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray analysis. The mean size of the Pt particles was found to be 10.7 nm. The general aspects of the electrochemical behavior were studied by cyclic voltammetry in 1 mol L-1 HClO4 aqueous solution. The response of these electrodes in relation to the oxidation of formaldehyde and methanol in acidic media was also studied.

Spectrophotometric determination of diclofenac in pharmaceutical preparations assisted by microwave oven

In this work, an effective and low-cost method for the determination of sodium or potassium diclofenac is proposed in its pure form and in their pharmaceutical preparations. The method is based on the reaction between diclofenac and tetrachloro-p-benzoquinone (p-chloranil), in methanol medium. This reaction was accelerated by irradiating of reactional mixture with microwave energy (1100 W) during 27 seconds, producing a charge transfer complex with a maximum absorption at 535 nm. The optimal reaction conditions values such as reagent concentration, heating time and stability of the reaction product were determined. Beer's law is obeyed in a concentration range from of 1.25x10-4 to 2.00x10-3 mol l-1 with a correlation coefficient of 0.9993 and molar absorptivity of 0.49 x10³ l mol-1 cm-1. The limit of detection (LOD) was 1.35x10-5 mol l-1 and the limit of quantification (LOQ) was 4.49x10-5 mol l-1. In the presence of the common excipients, such as glucose, lactose, talc, starch, magnesium stearate, sodium sulphite, titanium dioxide, polyethyleneglycol, polyvinylpirrolidone, mannitol and benzilic alcohol no interferences were observed. The analytical results obtained by applying the proposed method compare very favorably with those given by the United States Pharmacopeia standard procedure. Recoveries of diclofenac from various pharmaceutical preparations were within 95.9% to 103.3%, with standard deviations ranging from 0.2% to 1.8%.

Isolation of lignans glycosides from Alibertia sessilis (Vell.) K. Schum. (Rubiaceae) by preparative high-performance liquid chromatography

Enantiomeric aglycone lignans contained in a mixture were separated from a fraction of the extract of the stems of Alibertia sessilis (Vell.) K. Schum. (Rubiaceae) by preparative high-performance liquid chromatography. An efficient and fast separation can be achieved with methanol-water (30:70, v/v). Their structures were identified as (+)-lyoniresinol 3alpha-O-beta-glucopyranoside and (-)-lyoniresinol 3alpha-O-beta-glucopyranoside, being reported for the first time in Rubiaceae.

Spectrophotometric determination of metronidazole through Schiff's base system using vanillin and PDAB reagents in pharmaceutical preparations

Two simple sensitive and reproducible spectrophotometric methods have been developed for the determination of metronidazole either in pure form or in their tablets. The proposed methods are based on the reduction of the nitro group to amino group of the drug. The reduction of metronidazole was carried out with zinc powder and 5 N hydrochloric acid at room temperature in methanol. The resulting amine was then subjected to a condensation reaction with aromatic aldehyde namely, vanillin and p-dimethyl amino benzaldehyde (PDAB) to yield yellow colored Schiff's bases. The formed Schiff's bases are quantified spectrophotometrically at their absorption maxima at 422 nm for vanillin and 494 nm for PDAB. Beer's law was obeyed in the concentration ranges 10 to 65 µg mL-1 and 5 to 40 µg mL-1 with a limit of detection (LOD) of 0.080 µg mL-1 and 0.090 µg mL-1 for vanillin and PDAB, respectively. The mean percentage recoveries were found to be 100.05 ± 0.37 and 99.01 ± 0.76 for the two methods respectively. The proposed methods were successfully applied to determine the metronidazole in their tablet formulations and the results compared favorably to that of reference methods. The proposed methods are recommended for quality control and routine analysis.